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United States Patent |
6,020,456
|
Brunelle
,   et al.
|
February 1, 2000
|
Copolyetherimides with resistance to high temperatures
Abstract
Copolyetherimides are prepared by conventional means from hindered diamines
such as the isomeric methyl-4,6-diethyl-1,3-phenylenediamines and
bis(2-chloro-4-amino-3,5-diethylphenyl)methane. They have unusually high
glass transition temperatures.
Inventors:
|
Brunelle; Daniel Joseph (Burnt Hills, NY);
Grubb; Tina Lynn (Hattiesburg, MS);
Tullos; Gordon Lee (Hattiesburg, MS)
|
Assignee:
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General Electric Company (Schenectady, NY)
|
Appl. No.:
|
186705 |
Filed:
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November 6, 1998 |
Current U.S. Class: |
528/353; 525/436; 528/350 |
Intern'l Class: |
C08G 018/30; C08L 079/08 |
Field of Search: |
528/353
|
References Cited
U.S. Patent Documents
4550156 | Oct., 1985 | Gallagher | 528/185.
|
4680373 | Jul., 1987 | Gallagher et al. | 528/185.
|
5189115 | Feb., 1993 | Melquist | 525/420.
|
5608013 | Mar., 1997 | Matsuura et al. | 525/422.
|
Foreign Patent Documents |
0336998 | May., 1988 | EP.
| |
Other References
Ulery et al., "Highly Soluble Polyimides From Sterically Hindered
Diamines," Polym. Prep., , 38, 182-3 (1997).
|
Primary Examiner: Woodward; Ana
Attorney, Agent or Firm: Brown; S. Bruce, Johnson; Noreen C.
Parent Case Text
This application is a division of application Ser. No. 08/893,596, filed
Jul. 14, 1997, U.S. Pat. No. 5,917,005 which is hereby incorporated by
reference in its entirety.
Claims
What is claimed is:
1. A copolyetherimide comprising structural units of the formulas
##STR7##
wherein: Q is a divalent aliphatic or aromatic radical and A.sup.1 is a
divalent radical of the formula
##STR8##
A.sup.2 is m- or p-phenylene or a bis(alkylene)polydiorganosiloxane
radical or has the formula
##STR9##
X is O, S or NR.sup.4 ; R.sup.1 is an alkyl radical having from 2 to about
10 carbon atoms;
each R.sup.2 is independently C.sub.1-6 alkyl or halo;
R.sup.3 is C.sub.1-3 gem-alkylene;
R.sup.4 is hydrogen or C.sub.1-6 alkyl;
each of m, n and p is independently 0 or 1; and
z is 0 or 1.
2. The copolyetherimide according to claim 1 comprising about 10-90 mole
percent of units of formula I.
3. The copolyetherimide according to claim 1 wherein A.sup.2 is m-phenylene
or p-phenylene.
4. The copolyetherimide according to claim 3 wherein said units of formula
I have the formula
##STR10##
and said units of formula III have the formula
##STR11##
5. A copolyetherimide according to claim 1 wherein A.sup.1 has the formula
wherein z is 0 or 1.
6. The copolyetherimide according to claim 5 wherein said units of formula
I have the formula
##STR12##
and said units of formula III have the formula
##STR13##
7. The copolyetherimide according to claim 1 wherein A.sup.1 has the
formula
8. The copolyetherimide according to claim 7 wherein said units of formula
I have the formula and said units of formula III have the formula
##STR14##
Description
BACKGROUND OF THE INVENTION
This invention relates to polyetherimides. More particularly, it relates to
polyetherimides having extremely good resistance to high temperatures.
Polyetherimides are well known commercially available polymers having
advantageous properties including thermal oxidative resistance, good
mechanical strength, excellent electrical properties and good chemical
resistance. Commercially available polyetherimides include those of the
type which may be prepared by the reaction of such aromatic amines as m-
and p-phenylenediamine with bis(ether anhydrides) such as
2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, hereinafter
sometimes designated "BPADA" for brevity. Their temperature stability is
high, as shown by a glass transition temperature in the range of
215-220.degree. C.
It is of interest, however, to prepare polyetherimides having still better
resistance to high temperatures. Glass transition temperatures above
250.degree. C. would be especially desirable.
SUMMARY OF THE INVENTION
The present invention provides a genus of polyetherimides having extremely
good resistance to high temperatures. The glass transition temperatures of
these new polymers typically range from about 250.degree. C. to as high as
300.degree. C.
In one of its aspects, the invention is directed to copolyetherimides
comprising structural units of the formula
and
##STR1##
wherein Q is a divalent aliphatic or aromatic radical and A.sup.1 is a
divalent radical of the formula
##STR2##
wherein R.sup.1 is an alkyl radical having from 2 to about 10 carbon
atoms, each R.sup.2 is independently C.sub.1-6 alkyl or halo, R.sup.3 is
C.sub.1-3 gem-alkylene 3 and each of m, n and p is independently 0 or 1;
and A.sup.2 is m- or p-phenylene or a bis(alkylene)polydiorganosiloxane
radical or has the formula
##STR3##
wherein X is O, S or NR.sup.4, z is 0 or 1 and R.sup.4 is hydrogen or
C.sub.1-6 alkyl.
DETAILED DESCRIPTION; PREFERRED EMBODIMENTS
The preferred Q radical in the polyetherimides of this invention has the
formula
##STR4##
which may be considered as being derived from BPADA (preferably) or its
2,3-isomer.
The A.sup.1 radical has formula II in which each R.sup.1 value is an alkyl
radical having from form 2 to about 10 and preferably 2-3 carbon atoms.
Ethyl radicals are most preferred. The R.sup.2 values, when present, are
C.sub.1-6 alkyl or halo, especially methyl or chloro. R.sup.3, when
present, is a C.sub.1-3 gem-alkylene radical; that is, one in which both
free valence bonds are attached to the same carbon atom. It is preferably
methylene.
As will be apparent from formula II, the A.sup.1 radical may be monocyclic
(m is 0) or bicyclic (m is 1). Further, the free valence bonds (or the
single free valence bond and the bond connected to R.sup.3) may be in the
para or meta positions.
The preferred A.sup.1 radicals are, first, the two isomeric structures in
which m is 0, the R.sup.1 radicals are ethyl in the 4- and 6-positions,
R.sup.2 is methyl in the 2- or 5-position, n is 1 and the free valence
bonds are in the 1-and 3-positions, and second, the structure in which m
and p are each 1, each R.sup.1 is ethyl in an ortho-position to the free
valence bonds, R.sup.2 is chloro, R.sup.3 is methylene and the bonds
connected to R.sup.3 are in the para positions from the free valence
bonds.
These radicals correspond to the diamines having the respective formulas
##STR5##
wherein z is 0 or 1, and
##STR6##
Said diamines are respectively the two isomeric
methyl-4,6-diethyl-1,3-phenylenediamines (singly or in admixture) and
bis(2-chloro-4-amino-3,5-diethylphenyl)methane, which are respectively
commercially available from Albemarle Corporation as "Ethacure 100"
(mixture of isomers) and from Lonza Ltd. as "Lonzacure M-CDEA".
The polyetherimides of this invention include homopolyetherimides
(consisting of units of formula I. They also include copolyetherimides, a
preferred class of which comprises such units in combination with units of
formula III, wherein A.sup.2 is a non-silicon-containing organic or
bis(alkylene)polydiorganosiloxane radical or has formula IV. Suitable
A.sup.2 radicals include aromatic and especially C.sub.6-20 aromatic
radicals, as illustrated by m-phenylene, p-phenylene,
bis(4-phenylene)methane and bis(4-phenylene) ether radicals, and aliphatic
radicals, especially C.sub.2-20 aliphatic radicals such as ethylene,
trimethylene, hexamethylene and neopentylene. The aromatic radicals are
generally preferred, and especially the m-phenylene and p-phenylene
radicals; i.e., those present in m-phenylenediamine and
p-phenylenediamine.
The proportion of units of formula I in the co polyetherimides of this
invention is preferably sufficient to produce a polyetherimide having a
glass transition temperature of at least about 230.degree. C. About 10-90
mole percent of units of formula I is typical, with about 40-60 mole
percent often being preferred.
The polyetherimides of this invention may be prepared by conventional
methods, conducted under art-recognized conditions. One generally
applicable method is the reaction of at least one appropriate diamine with
at least one tetracarboxylic acid or dianhydride or other functional
derivative (e.g., tetrahalide) thereof. Preparation may also be by the
reaction of at least one bisphenol salt, typically the disodium salt, with
at least one appropriate bis(halo- or nitro phthalimide), most often in a
solvent of low polarity and in the presence of a thermally stable phase
transfer catalyst such as a hexaalkylguanidinium halide.
The preparation of the polyetherimides of this invention is illustrated by
the following examples. Molecular weights are weight average and were
determined by gel permeation chromatography.
EXAMPLE 1
Anhydrous bisphenol A disodium salt was prepared by the reaction of
bisphenol A with an equimolar proportion of 50% aqueous sodium hydroxide
solution followed by removal of water by azeotropic distillation in
xylene.
"Ethacure 100" diamine (17.83 g, 100 mmol) was added in a nitrogen
atmosphere to a solution of 36.51 g (200 mmol) of 4-chlorophthalic
anhydride in 200 ml of o-dichlorobenzene at 135.degree. C. The solution
turned brown and then became colorless when the addition was complete.
About 20 mg of 4-dimethylaminopyridine was added as a catalyst and the
solution was heated at 165.degree. C. for 1 hour and under reflux for 3
hours. High pressure liquid chromatographic analysis indicated
disappearance of the reactants with formation of four isomeric products.
The solution was concentrated to about 100 ml, cooled and poured into
petroleum ether, affording the desired bis(chlorophthalimide) mixture in
85% yield.
A 50-ml 3-necked flask was oven dried, transferred to a nitrogen dry box
and charged with 2.764 g (10.15 mmol) of anhydrous bisphenol A disodium
salt and 5.074 g (10 mmol) of the above-prepared bis(chlorophthalimide)
mixture. The flask was capped and fitted with a condenser, nitrogen
introduction means and mechanical stirrer. o-Dichlorobenzene, 30 ml, was
added and the mixture was heated to reflux and about 5 ml of solvent
removed by distillation. Hexa-n-propylguanidinium chloride, 175 mg (0.5
mmol), was added over one minute in solution in about 1 ml of
o-dichlorobenzene, whereupon a vigorous exothermic reaction occurred with
dissolution of solids and thickening of the solution. The mixture was
sampled and analyzed periodically. When molecular weight growth was
complete, the reaction was quenched with acetic acid and cooled to room
temperature.
The product solution was diluted with methylene chloride, washed with 3%
aqueous hydrochloric acid solution and water several times and vacuum
stripped to remove methylene chloride. The product polyetherimide was then
isolated by precipitation into methanol and filtration. It had a weight
average molecular weight of 137,500 and a glass transition temperature of
295.degree. C. after a 15-minute reaction. The molecular weight after a
5-minute reaction was 112,000.
EXAMPLE 2
The procedure of Example 1 was repeated, substituting anisole for the
o-dichlorobenzene as solvent. After reaction periods of 5, 15 and 30
minutes, the product polyetherimides had weight average molecular weights
of 24,000, 81,000 and 112,000, respectively.
EXAMPLE 3
The procedure of Example 1 was repeated, using a mixture containing
equimolar proportions of the mixed bis(chlorophthalimides) employed in
Example 1 and the bis(chlorophthalimide) of m-phenylenediamine. After 5
and 15 minutes of reaction, the product copolyetherimides had weight
average molecular weights of 85,000 and 102,000, respectively.
EXAMPLE 4
A round-bottomed flask equipped with a mechanical stirrer and a nitrogen
purge line was charged with 10.238 g (19.671 mmol) of BPADA, 3.507 g
(19.671 mmol) of "Ethacure 100" diamine and 44 ml of N-methylpyrrolidone.
The mixture was stirred for 24 hours under nitrogen, after which 20 ml of
xylene was added and the mixture was heated at 180.degree. C. for 10
hours. The resulting polyetherimide was precipitated into methanol,
filtered, washed with methanol and dried under vacuum. It had a molecular
weight of 54,100.
EXAMPLE 5
The procedure of Example 4 was repeated, using a mixture containing
equimolar proportions of "Ethacure 100" diamine and m-phenylenediamine. A
corresponding copolyetherimide was obtained.
EXAMPLE 6
The procedure of Example 1 was repeated, substituting "Lonzacure M-CDEA"
diamine for the "Ethacure 100" diamine on an equimolar basis. The
resulting polyetherimide had a glass transition temperature of 252.degree.
C.
EXAMPLE 7
The procedure of Example 4 was repeated, substituting "Lonzacure M-CDEA"
diamine for the "Ethacure 100" diamine on an equimolar basis. A similar
product was obtained.
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